JPH03504505A - Synthesis of hydrocarbylamine - Google Patents

Synthesis of hydrocarbylamine

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JPH03504505A
JPH03504505A JP2502996A JP50299690A JPH03504505A JP H03504505 A JPH03504505 A JP H03504505A JP 2502996 A JP2502996 A JP 2502996A JP 50299690 A JP50299690 A JP 50299690A JP H03504505 A JPH03504505 A JP H03504505A
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hydrogenation
ozone
polyolefin
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ブラックボロー，ジョン　リチャード
ペレッティ，レジス
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ビーピー　ケミカルズ　リミテッド
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/54—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/066—Arylene diamines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/067—Polyaryl amine alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound

Abstract

(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 ヒドロカルビルアミンの合成 この発明は、潤滑油またはガソリン活性剤として使用するのに適切なヒドロカル ビルアミンを製造する方法に関する。[Detailed description of the invention] Synthesis of hydrocarbylamine This invention describes hydrocarbons suitable for use as lubricating oil or gasoline activators. The present invention relates to a method for producing bilamin.

長鎖しドロカルピル鎖を有する窒素誘導体を製造する方法は周知である。Ｓえば Ｇ８−Ａ−１１７２Ｊ３１８号（モノサンド）には、アルコールの存在下にオゾ ンを用いてポリオレフィンを酸化した後、酸化生成物をカルボニル化合物に変換 し、カルボニル化合物をオゾン分解生成物からのその分ｊＩｉ後にアミンと反応 させることによりシッフ塩基を得ることによるシッフ塩基の製造方法が記載され ている。Methods for producing nitrogen derivatives with long drocarpylic chains are well known. If it's S G8-A-1172J318 (Monosand) contains ozone in the presence of alcohol. After oxidizing polyolefins using carbon dioxide, the oxidation products are converted to carbonyl compounds. and the carbonyl compound is reacted with the amine after that fraction jIi from the ozonolysis product. A method for producing Schiff bases is described by obtaining Schiff bases by ing.

アミンとの反応の前にオゾン分解生成物からカルボニル化合物を分離および／ま たは精製することがこのように必要なことにより、この方法は商業的に発展不可 能なものとなっていると考えられる。Separation and/or removal of carbonyl compounds from ozonolysis products prior to reaction with amines This requirement for purification makes this method commercially unfeasible. It is thought that it has become possible.

他の方法はＥＰ−＾−２４４６１６号（ＢＡＳＦ　　ＡＧ）に記載されているも のであるが、この場合は、ポリブテンを水素ホルミル化に供し、この結果得られ たオキソ生成物の混合物を（ａ）マンニッヒ反応または（ｂ）水素アミノ化反応 に供する。Other methods are described in EP-^-244616 (BASF AG). In this case, polybutene is subjected to hydrogen formylation, and the resulting The mixture of oxo products obtained is subjected to (a) Mannich reaction or (b) hydrogen amination reaction. Serve.

この反応は、水素アミン化生成物が、長鎖アルデヒド、テトラ並びに長鎖アルコ ールの混合物を伴うという欠点を有する。この種の生成物の混合物、特に長鎖ア ルコールの存在（これはマンニラし反応または水素アミノ化の前に分離されない ）は、生成物の複雑な混合物を与える。This reaction produces hydrogen amination products such as long chain aldehydes, tetra as well as long chain alcohols. It has the disadvantage of involving a mixture of tools. Mixtures of products of this type, especially long-chain aliphatic Presence of alcohol (which is not separated before the mannilla reaction or hydrogen amination) ) gives a complex mixture of products.

更に、長鎖アルコールは、例えば潤滑油添加物またはガソリン活性剤として使用 する場合、アミノ化最終生成物に対して有害な効果を有し得る。Additionally, long chain alcohols can be used as lubricating oil additives or gasoline activators, for example. If so, it can have a deleterious effect on the final aminated product.

この種の従来技術による方法に伴う問題点を、（ａ）　０Ｂ−Ａ−１１７２８１ ８号の分離工程およびＥ−Ａ−２４４６１６号の水素ホルミル化工程を回避する ことにより緩和し得ることをこの度突き止めた。The problems associated with this type of prior art method are as follows: (a) 0B-A-117281 Avoiding the separation step of No. 8 and the hydrogen formylation step of No. EA-244616 We have now discovered that this can be alleviated by

よって本発明は、ポリオレフィンから長鎖アルキルアミンを製造する方法であっ て、前記方法は、（ａ）溶剤の存在下に３３０〜２０００の範囲の分子量を有す るポリオレフィンとオゾンとを反応させ、（ｂ）　（ａ）に由来するオゾン分解 生成物をそこに形成されるカルボニル化合物を分離および／または単離すること なく第１ヒドロカルビルアミンと反応させてイミンを形成し、（Ｃ）水素添加触 媒の存在下に工程（ｂ）に由来するイミンを水素添加し、 （ｄ）工程（Ｃ）で形成された水素添加生成物から長鎖アルキルアミンを回収す ることからなる。Therefore, the present invention is a method for producing long-chain alkylamines from polyolefins. (a) having a molecular weight in the range of 330 to 2000 in the presence of a solvent; (b) Ozone decomposition originating from (a) separating and/or isolating the carbonyl compounds formed therein; (C) reacting with a first hydrocarbyl amine to form an imine; hydrogenating the imine derived from step (b) in the presence of a medium; (d) recovering long chain alkyl amines from the hydrogenation product formed in step (C); It consists of things.

オゾン分解されるポリオレフィンを適切には０２〜Ｃ４のオレフィンの重合体ま たはその共重合体とし、３３０〜２０００、好ましくは５００〜１５００の範囲 の分子量を有するものとする。これらの内、ポリブテン、特にポリイソブチンを 顕著な割合で含有するもの、すなわちハイビス、ナプビス並びにウルトラビス（ 全て登録商標、例えばＢＰケミカルス）が好適である。The polyolefin to be ozonolyzed is suitably a polymer of 02 to C4 olefins. or a copolymer thereof, in the range of 330 to 2000, preferably 500 to 1500. It shall have a molecular weight of Among these, polybutene, especially polyisobutyne Those containing significant proportions, namely Hivis, Napvis and Ultravis ( All registered trademarks, such as BP Chemicals) are preferred.

前記工程（ａ）におけるポリオレフィンのオゾン分解は、適切には溶剤中のポリ オレフィンの溶液を介して、付加的な希釈剤の存在下または非存在下に、気相中 でのオゾンのバブリングによって行う、使用し得る溶剤の例には、アルコールお よび炭化水素、好ましくは脂肪族、直鎖状アルコール（鎖中に１〜１２の炭素原 子を有する）が包含される。アルコールの場合、これらは好ましくは鎖中に１〜 ４の炭素原子を有する。The ozonolysis of the polyolefin in step (a) is suitably carried out using a polyolefin in a solvent. Via a solution of the olefin, in the presence or absence of an additional diluent, in the gas phase Examples of solvents that can be used include alcohol and and hydrocarbons, preferably aliphatic, linear alcohols (with 1 to 12 carbon atoms in the chain) ) is included. In the case of alcohols these are preferably 1 to 1 in the chain. It has 4 carbon atoms.

オゾン分解温度は、適切には一７０〜＋５０℃、好ましくは一３０〜＋３０℃、 最も好ましくは一１０〜＋３０℃とする。この反応は発熱的であり、したがって 注意を払い、必要ならば冷却により反応温度が５０℃を越えないことを確実にす べきである。The ozone decomposition temperature is suitably -70 to +50°C, preferably -30 to +30°C, Most preferably the temperature is -10 to +30°C. This reaction is exothermic and therefore Take care and ensure that the reaction temperature does not exceed 50°C by cooling if necessary. Should.

溶剤は適切には反応混合物中に、ポリオレフィン反応体に対して１：１〜１０： １の重量比で存在するものとする。The solvent is suitably present in the reaction mixture in a ratio of 1:1 to 10:1 to polyolefin reactant. It shall be present in a weight ratio of 1.

この反応については、与えられた温度および圧力で反応させるオゾン対オレフィ ンの比率を、爆発混合物が形成されないよう確実にすることが必須である０種々 の反応条件についての爆発限界は当業者に周知である。For this reaction, ozone vs. olefin reacted at a given temperature and pressure. It is essential to ensure that no explosive mixture is formed. Explosive limits for reaction conditions are well known to those skilled in the art.

工程（ａ）に由来するオゾン分解生成物を、工程（ｂ）で第１アミンと接触させ る。この工程については、第１アミンとの反応について、オゾン分解生成物を直 接、すなわち、前に何ら分離工程を置くことなく使用する。オゾン分解生成物と 第１アミンとを接触させる前に、（ｉ）不活性ガス、例えば窒素をこれを介して 散布することにより中の全ゆる過剰なオゾンを除去し、（ｉｉ）水によりオゾン 分解生成物を洗浄して例えばアセトンのような全ゆる低沸点画分の除去を図るの が好適である。contacting the ozonolysis product from step (a) with a primary amine in step (b); Ru. For this step, ozone decomposition products are directly removed for reaction with primary amines. used directly, ie without any prior separation step. ozone decomposition products and (i) passing an inert gas, e.g. nitrogen, before contacting the primary amine; Remove all excess ozone by spraying, (ii) remove ozone with water. The decomposition products are washed to remove all low boiling fractions such as acetone. is suitable.

オゾン分解生成物との反応に使用する第１ヒドロカルビルアミンは、脂肪族、脂 環式または芳香族の性状とし得る１以上のモノ、ジ並びにポリアミンとし得る。The primary hydrocarbylamine used in the reaction with the ozonolysis product is an aliphatic, fatty It can be one or more mono-, di-, and polyamines that can be cyclic or aromatic in nature.

この発明の化合物を調製するのに使用し得る典型的なアミンの例には、ジエチレ ントリアミン、ジ（メチルエチレン）トリアミン、トリエチレンテトラミン、ト リ（メチルエチレン）テトラミン、トリ（エチルエチレン）テトラミン、テトラ エチレンペンタミン、ペンタエチレンへキサミン、エチレンジアミン、ヘキサメ チレンジアミン、Ｏ−７二二レンジアミン、ｍ−７二二レンジアミン、ｐ−７二 二レンジアミン、アルキル置換０−１ｍ−１並びにｐ−フ二二レンジアミン、ジ メチルアミノメチルアミン、ジメチルアミノエチルアミン、ジメチルアミノプロ ピルアミン、ジメチルアミノブチルアミン、ジメチルアミノへブチルアミン、ジ エチルアミノメチルアミン、ジエチルアミノプロビルアミン、ジエチルアミノア ミルアミン、ジプロピルアミノ１０ピルアミン、メチルプロピルアミノアミルア ミン、１０ピルブチルアミノエチルアミン、ジメチレントリアニリンメチレンジ アニリン、ポリメチレンアニリン並びにポリアルキルメチレンアニリンがある。Examples of typical amines that can be used to prepare compounds of this invention include diethyl triamine, di(methylethylene)triamine, triethylenetetramine, triamine Li(methylethylene)tetramine, tri(ethylethylene)tetramine, tetra Ethylenepentamine, pentaethylenehexamine, ethylenediamine, hexame ethylene diamine, O-7 22 diamine, m-7 22 diamine, p-7 di di-diamine, alkyl-substituted 0-1m-1 and p-ph-di-di diamine, di-diamine, Methylaminomethylamine, dimethylaminoethylamine, dimethylaminopro Pyramine, dimethylaminobutylamine, dimethylaminohebutylamine, di Ethylaminomethylamine, diethylaminopropylamine, diethylaminoa Mylamine, dipropylamino 10-pylamine, methylpropylaminoamylamine amine, 10 pyrbutylaminoethylamine, dimethylene trianiline methylene diamine Aniline, polymethyleneaniline and polyalkylmethyleneaniline.

工程（ａ）に由来するオゾン分解生成物と工程（ｂ）の第１アミンとの反応は、 適切には例えば５０〜２００℃の範囲の温度で行う、第１アミンとのこの反応は 、反応混合物中に既に存在する溶剤の全ゆる随伴する揮発と共に、反応の際に形 成される水の連続的な除去によって行う。The reaction of the ozonolysis product from step (a) with the primary amine of step (b) is This reaction with a primary amine, suitably carried out at a temperature in the range of e.g. , during the reaction, with any accompanying volatilization of the solvent already present in the reaction mixture. This is done by continuous removal of the water produced.

この反応において、オゾン分解生成物対第１アミンの比率は、適切には１：１〜 １０００：１、好ましくは１：１〜５：１とする。In this reaction, the ratio of ozonolysis products to primary amines is suitably from 1:1 to The ratio is 1000:1, preferably 1:1 to 5:1.

工程（ｂ）の反応の生成物はヒドロカルビルイミンである。The product of the reaction of step (b) is a hydrocarbylimine.

この生成物中に共に存在するのは、水および溶剤、特に前記工程（ａ）に使用し たものである。Also present in this product are water and a solvent, in particular those used in step (a) above. It is something that

例えばろ過および／まなは分別蒸留によって、水および溶剤をイミン生成物から 分離する。Water and solvent are removed from the imine product, for example by filtration and/or fractional distillation. To separate.

工程（ｂ）に由来する分離されたイミン生成物は、その後水素添加して所望のア ミンを作成する。The separated imine product from step (b) is then hydrogenated to obtain the desired amine. Create Min.

イミンの水素添加は、均一または不均一条件下で行うことができる。Hydrogenation of imines can be carried out under homogeneous or heterogeneous conditions.

水素添加は、ラネイニッケル、コバルト、ルテニウム、ロジウム、イリジウム、 プラチナ特にカーボン上のプラチナ、カーボン上のパラジウム、シリカ上のパラ ジウム等のような触媒を使用して行う。Hydrogenation includes Raney nickel, cobalt, ruthenium, rhodium, iridium, Platinum, especially platinum on carbon, palladium on carbon, and palladium on silica. This is done using a catalyst such as nickel or the like.

水素添加反応は、適切には２０　Ｍ　Ｐ　ａまで、好ましくは１０ＭＰａまで、 更に好ましくは８ＭＰａ、ｔでの圧力で行う。The hydrogenation reaction is suitably carried out at up to 20 MPa, preferably up to 10 MPa, More preferably, it is carried out at a pressure of 8 MPa, t.

水素添加反応は、適切には０〜２００℃、好ましくは５０〜１５０℃の温度で行 う。The hydrogenation reaction is suitably carried out at a temperature of 0 to 200°C, preferably 50 to 150°C. cormorant.

不均一条件下で水素添加反応を行う場合、触Ｕ残渣の除去を促進する。この目的 のなめ、アミン生成物の溶剤抽出を使用することができる。好適な溶剤は脂肪族 アルコールまたは炭化水素である。When the hydrogenation reaction is carried out under heterogeneous conditions, the removal of U residues is facilitated. this purpose As a result, solvent extraction of the amine product can be used. Preferred solvents are aliphatic Alcohol or hydrocarbon.

実際、単一の反応器中で、オゾン分解生成物のイミノ化およびこのようにして形 成されたイミンの対応するアミンへの水素添加を行うことが可能であり、これに より工程（ｂ）の生成物の分離／精製の必要性を回避する。よって、前記イミノ 化工程（ｂ）および前記水素添加工程（Ｃ）について推奨される条件を、中間体 イミンを回収することなく単一反応器中で順次に使用することができる。典型的 には、最初にイミノ化反応を進行させて６０％ｗ　／　ｗまでのオゾン分解生成 物をイミンに変換させ、その後間−の反応器中でこのようにして形成された粗製 イミノ化生成物を何ら分離工程を置くことなく水素添加することによりこれを行 うことができる。In fact, in a single reactor, the imination of ozonolysis products and thus the formation of Hydrogenation of the prepared imine to the corresponding amine can be carried out, which thereby avoiding the need for separation/purification of the product of step (b). Therefore, the imino The conditions recommended for the hydrogenation step (b) and the hydrogenation step (C) are The imine can be used sequentially in a single reactor without recovery. typical To do this, first proceed with the imination reaction to generate up to 60% w/w of ozone decomposition. the crude product thus formed in an intermediate reactor. This is done by hydrogenating the imination product without any separation step. I can.

その他、水素添加触媒を適切に選択することにより、カルボニル化合物のイミノ 化およびイミンの水素添加の双方を、形成された全ゆるイミンが瞬間的にアミン に水素添加されるよう実質的に同時に行うことができる。よって、水素添加工程 の開始前に、何らかの顕著な量のイミンが形成されるのを待つ必要はない。In addition, by appropriately selecting a hydrogenation catalyst, carbonyl compounds can be Both hydrogenation and hydrogenation of imines are carried out so that all the imines formed are instantaneously converted to amines. hydrogenation can be carried out substantially simultaneously. Therefore, the hydrogenation process There is no need to wait for any significant amount of imine to be formed before starting.

このようにして所望のアミンは、触媒をろ別し、蒸留によりろ液から溶剤を除去 することにより水素添加の反応生成物から回収することができる。The desired amine is thus obtained by filtering off the catalyst and removing the solvent from the filtrate by distillation. By doing so, it can be recovered from the reaction product of hydrogenation.

本発明のヒドロカルビルアミンは、潤滑油添加物、燃料添加物並びにガソリン洗 浄剤として使用することができる。The hydrocarbyl amines of the present invention can be used as lubricating oil additives, fuel additives and gasoline detergents. Can be used as a cleaning agent.

以下の実施例を参照して本発明を更に説明する。The invention will be further illustrated with reference to the following examples.

衷簾±ユ 歪」」ｄｌゑ Ａ（ａ） ガス分散装置をその基部に備え均−熱ジャケットを備える管状ガラス容器に、１ ００ｇのＭｎ１ＯＯＯのポリイソブチン（ＮＡＰＶＩＳ　１０　、ＲＴＨ）およ び１００ｍ１のｎ−ヘキセンを入れた。その後、１５℃にて時間当り０．１３モ ルの速度で、ポリイソブチン溶剤混合物中にオゾンを通過させた。４時間後、オ ゾンの供給を停止し、短い時間（２分）反応混合物に対して窒素を通過させ、い まやオゾン分解生成物を含有する容器中の全ゆる未反応オゾンを除去した。Curtain ± Yu Distortion” dlゑ A(a) In a tubular glass vessel equipped with a gas dispersion device at its base and an equalizing jacket, 1 00 g of Mn100 polyisobutyne (NAPVIS 10, RTH) and and 100 ml of n-hexene. After that, 0.13 mole per hour at 15℃ The ozone was passed through the polyisobutyne solvent mixture at a rate of 1. 4 hours later, Stop the nitrogen supply and briefly (2 min) pass nitrogen through the reaction mixture. All unreacted ozone in the container containing the ozonolysis products was removed.

（ｂ） その後０．２モルのジメチルアミノプロピルアミンをオゾン分解生成物に添加し 、一方窒素の通過を更に２分間続けた。(b) Then 0.2 mol of dimethylaminopropylamine was added to the ozonolysis product. , while the nitrogen passage continued for an additional 2 minutes.

その後容器の内容物を、コンデンサを備えたガラス反応器（５００ｍｌ容量）に 移した０反応器の内容物を２時間還流（７１℃）し、最終的に油浴を使用して真 空下１４０℃にて回転エバポレータ中で反応混合物を蒸発させた。蒸発の後に残 留する不揮発性残渣はイミン中間体であり、これは黄色で１．８％ｗ　／　ｗの 窒素を含有し、１１５ｇの生成物が約６４％モルのイミン収率で回収された。The contents of the container were then transferred to a glass reactor (500 ml capacity) equipped with a condenser. The contents of the transferred zero reactor were refluxed (71°C) for 2 hours and finally evaporated using an oil bath. The reaction mixture was evaporated in a rotary evaporator at 140° C. under vacuum. left behind after evaporation The non-volatile residue that evaporates is the imine intermediate, which is yellow in color and has a concentration of 1.8% w/w. Containing nitrogen, 115 g of product was recovered with approximately 64% molar imine yield.

Ｂ　（ａ） 前記Ａ　（ａ＞で使用したものの約５倍大きい直径を有する管状ガラス反応器中 に、６５０ｇのＭｎ１ＯＯＯのボ９リイソブテンおよびｎ−ヘキサンとメタノー ル（それぞれ３００ｍ１）との混合物を入れた。少量の空気を含有するオゾンを 、激しく攪拌しながらポリイソブチン／溶剤混合物を通過させた。この操作の際 、ｎ−ヘキサンとメタノールとの５０１５０　ｗ　ｔ％混合物の画分（合計３０ ０ｍ１）を、時間と共に更に添加した０反応は６．５時間進行させた。その後オ ゾン供給を停止し、反応混合物に窒素を散布してその中の全ゆる未反応オゾンを 除去した。その後反応混合物に水（３００ｍｌ＞を添加した０反応器の全内容物 をその後別の容器に移し、水相を分離した。これは容易に起こり、水相を分離し た。B (a) In a tubular glass reactor having a diameter approximately 5 times larger than that used in A above (a>) 650 g of Mn100 bo-9-lysobutene and n-hexane and methanol. (300 ml each). Ozone containing a small amount of air , the polyisobutyne/solvent mixture was passed through with vigorous stirring. During this operation , a fraction of 50150 wt% mixture of n-hexane and methanol (total 30 The reaction was allowed to proceed for 6.5 hours with additional additions of 0 ml) over time. Then Stop the ozone supply and sparge the reaction mixture with nitrogen to remove any unreacted ozone therein. Removed. The total contents of the reactor were then added with water (300 ml) to the reaction mixture. was then transferred to another container and the aqueous phase was separated. This happens easily and separates the aqueous phase. Ta.

（ｂ） ２２０ｇの未精製有機生成物を、８００ｍ１のトルエンおよび２００ｍ１のトル エン中の２４．７４ｇの市販のテトラエチレンペンタミンと混合した。全混合物 を加熱して沸騰させ、４時間後に４００ｍ１の溶剤を除去しな、油ポンプによる 真空下１４０℃で回転エバポレータ中で残留する溶剤を除去しな。(b) 220 g of crude organic product was added to 800 ml of toluene and 200 ml of toluene. Mixed with 24.74 g of commercially available tetraethylenepentamine in Ene. whole mixture Heat to a boil and remove 400ml of solvent after 4 hours using an oil pump. Remove residual solvent in a rotary evaporator at 140°C under vacuum.

エバポレータから２４０ｇの生成物が回収され、これは３．１％ｗ　／　ｗの窒 素を含有し、約６６％モルのイミン収量に相当する。240 g of product was recovered from the evaporator, containing 3.1% w/w nitrogen. This corresponds to an imine yield of approximately 66% molar.

前記ＡおよびＢプロセスの比較は、類似するイミン収量について、攪拌しない反 応器より攪拌した反応器の方が必要なオゾンが非常に少ないことを示す。A comparison of the A and B processes above shows that for similar imine yields, the unstirred reaction This shows that much less ozone is required in the stirred reactor than in the reactor.

土工Ｚ立水工盪迦 前記実施例１（Ａ）の手順に由来する７０ｇのイミン生成物を、８０ｍ１のシク ロヘキサンと共に機械的攪拌装置を備えた３００ｍ１容量の高圧オートクレーブ に入れた。２０ｍｌのエタノールと共に、５ｇのエタノールで洗浄した新鮮なラ ネイニッゲルの市販サンプルもオートクレーブに添加し、その後これを封止し、 水素により脱ガスした。オートクレーブの内容物を１５ＭＰａ（１５０バール） の水素雰囲気下で激しく撹拌し、９０℃に１９時間維持した。攪拌を停止し、オ ートクレーブの内容物を冷却した後、圧力を抜いた０反応混合物をろ過し、前記 実施例１（Ａ）のように回転エバポレータによりろ液を蒸発させた。得られた麦 わら色の残渣は、１８００−”〜１６００−”のスペクトル範囲の赤外線の無視 し得る吸収を示し、生成物中にイミンまたはカルボニル官能基が全く存在しない ことを示した。この生成物は１％ｗ　／　ｗの窒素含量を有していた。Earthworks Z standing water works 70 g of imine product from the procedure of Example 1(A) above was added to 80 ml of 300ml capacity high pressure autoclave with mechanical stirring device with lohexane I put it in. Fresh lab washed with 5 g of ethanol along with 20 ml of ethanol. A commercial sample of Neinigel was also added to the autoclave, which was then sealed and Degassed with hydrogen. The contents of the autoclave were heated to 15 MPa (150 bar) The mixture was stirred vigorously under a hydrogen atmosphere and maintained at 90° C. for 19 hours. Stop stirring and turn on. After cooling the contents of the totoclave, the depressurized reaction mixture was filtered and The filtrate was evaporated in a rotary evaporator as in Example 1(A). Obtained wheat Straw-colored residue ignores infrared radiation in the 1800-” to 1600-” spectral range absorption and the absence of any imine or carbonyl functionality in the product. It was shown that This product had a nitrogen content of 1% w/w.

寒豊■ノ ー工　でのイミノ　および　素・１口 ４０１ｇのポリブテン（Ｍｎ＝１３００）を、攪拌により４００ｍ１のｎ−オク タンおよび２５ｍ１のメタノールと混合し、空気中にて０．１３モル／時間のオ ゾンを攪拌混合物に対して３．５時間通過させ、その後５００ｍ１の水と反応体 とを混合し、混合物を水相と有機相とに分離した。水相を除去し、有機相と４８ ｇのジメチルアミノプロピルアミンとを、ディーン＆スタークサイドアームを備 えた水素添加反応器中で混合した０反応器の内容物を３時間還流し、ディーン＆ スタークサイドアームを介して水を除去した。その後、カーボン上のプラチナ（ Ｐｔ、５％ｗ／ｗ）３．５ｇを反応器に添加し、反応器をその内容物と共に水素 により１６０’Ｃで２．８ＭＰａ　（２８バール）に加圧した。激しく攪拌しつ つ２０時間に渡って水素添加反応を続けた。Kantoyo■ノ -Imino at the factory and raw 1 mouth 401 g of polybutene (Mn=1300) was converted into 400 ml of n-octane by stirring. 0.13 mol/h in air. Pass the zone over the stirred mixture for 3.5 hours, then add 500 ml of water and the reactants. and the mixture was separated into an aqueous phase and an organic phase. Remove the aqueous phase and combine with the organic phase g dimethylaminopropylamine and equipped with a Dean & Stark side arm. The mixed contents of the reactor were refluxed for 3 hours in a hydrogenation reactor prepared by Dean & Water was removed via the Stark side arm. Then platinum on carbon ( 3.5 g of Pt, 5% w/w) were added to the reactor and the reactor was flushed with hydrogen with its contents. Pressure was increased to 2.8 MPa (28 bar) at 160'C. Stir vigorously The hydrogenation reaction was continued for 20 hours.

その後反応器の内容物を取り出してろ過した。軽い画分の全てが除去され粘質の 残渣が後に残るまで、回転蒸留技術によりろ液を処理した。The contents of the reactor were then removed and filtered. All of the light fractions are removed and the viscous The filtrate was processed by rotary distillation technique until a residue remained behind.

粘質の残渣（１００℃で５６０ｃｓｔ）は、１．２％Ｗ／Ｗの窒素を含有し、痕 Ｍ量のみのカルボニルまたはイミンのバンドが生成物の赤外線スペクトルで検出 された（く１０モル％）。The viscous residue (560 cst at 100°C) contains 1.2% W/W nitrogen and no traces. Carbonyl or imine bands with only M amount detected in the infrared spectrum of the product (10 mol%).

Ｋま■旦 一工　でのイミノ　および　素添口 Ｍｎ＝１３００のポリブテンカルボニルの３６５ｇのイミンの混合物および前記 実施例２のプロセスにより調製したポリブテンカルボニルを、水素添加反応器中 で４５０ｍ１のｎ−オクタンおよび３ｇの５％ｗ　／　ｗのカーボン上のプラチ ナと混合した。１３０℃で２．０〜３．０ＭＰａ　（２０〜３０バール）の圧力 にて６時間の水素添加の後、サンプルを取り、１６５℃で１時間４ｍｍＨＨの圧 力で回転蒸留に供し、軽い両分を除去し、後に粘質の残渣を残した。残渣の赤外 線スペクトルは、小さいイミンバンドおよびカルボニルバンドを示した。K-day Imino and sozoeguchi in one construction A mixture of 365 g of imine of polybutene carbonyl with Mn=1300 and the above The polybutene carbonyl prepared by the process of Example 2 was placed in a hydrogenation reactor. 450ml of n-octane and 3g of 5% w/w platy on carbon mixed with na. Pressure of 2.0-3.0 MPa (20-30 bar) at 130°C After hydrogenation for 6 hours at It was subjected to rotary distillation under pressure to remove the light components and leave behind a sticky residue. residue infrared The line spectrum showed small imine and carbonyl bands.

バルク生成物の水素添加を更に６時間続け、サンプリング手順を繰り返した。サ ンプル残渣の赤外線スペクトル（前記したように回転蒸留の後）は、今度は痕跡 量のイミンバンドおよび顕著なカルボニルバンドを示した。Hydrogenation of the bulk product was continued for an additional 6 hours and the sampling procedure was repeated. sa The infrared spectrum of the sample residue (after rotary distillation as described above) now shows traces of It showed a large amount of imine bands and a prominent carbonyl band.

バルクの水素添加を更に６時間続けたが、今度は２７ｍ１のジメチルアミノプロ ピルアミンの存在下とし、前記したように再度サンプリング手順を繰り返した。Bulk hydrogenation was continued for another 6 hours, but now with 27 ml of dimethylaminopropylene. The sampling procedure was repeated again as described above in the presence of pyramine.

今回は、サンプル残渣の赤外線スペクトルからカルボニルバンドが殆ど完全に消 失したことが銘記された。This time, the carbonyl band almost completely disappeared from the infrared spectrum of the sample residue. I was reminded that I had lost it.

その後反応器中のバルク内容物をろ過し、回転蒸留技術により処理し、全ての軽 い未反応材料を除去し、その後に粘質の残渣を残した。残渣は薄い黄色であり、 約１６５％ｗ　／　ｗの塩基性窒素を含有していた。The bulk contents in the reactor are then filtered and treated by rotary distillation techniques to remove all light Any unreacted material was removed, leaving behind a sticky residue. The residue is pale yellow; It contained about 165% w/w basic nitrogen.

残渣のＮＭＲスペクトルはポリブテンポリアミンの存在を示した。NMR spectrum of the residue showed the presence of polybutene polyamine.

このサンプルは、カーボン触媒上のプラチナは、ポリブテンカルボニルより速く ポリブテンイミンを水素添加し、またアミンの存在下では、ポリブテンカルボニ ルの１工程水素アミノ化によってポリブテンポリアミンが製造され得ることを示 す。This sample shows that platinum on carbon catalyst is faster than polybutene carbonyl Hydrogenating polybutene imine and also in the presence of amines, polybutene carbonyl We show that polybutene polyamines can be produced by one-step hydrogen amination of vinegar.

国際調査報告 国際調査報告international search report international search report

Claims (10)

【特許請求の範囲】[Claims] １．ポリオレフィンから長鎖アルキルアミンを製造する方法であって、 （ａ）溶剤の存在下に３３０〜２０００の範囲の分子量を有するポリオレフィン とオゾンとを反応させ、（ｂ）（ａ）に由来するオゾン分解生成物をそこに形成 されるカルボニル化合物を分離および／または単離することなく第１ヒドロカル ビルアミンと反応させてイミンを形成し、（ｃ）水素添加触媒の存在下に工程（ ｂ）に由来するイミンを水素添加し、 （ｄ）工程（Ｃ）で形成された水素添加生成物から長鎖アルキルアミンを回収す る ことからなる前記方法。1. A method for producing a long-chain alkylamine from a polyolefin, the method comprising: (a) Polyolefin having a molecular weight in the range of 330 to 2000 in the presence of a solvent (b) react with ozone to form therein ozone decomposition products derived from (a); the first hydrocarbon without separating and/or isolating the carbonyl compound (c) step (c) in the presence of a hydrogenation catalyst. b) hydrogenating the imine derived from (d) recovering long chain alkyl amines from the hydrogenation product formed in step (C); Ru The method comprising: ２．オゾン分解されるポリオレフィンをＣ２〜Ｃ４のオレフィンの重合体または その共重合体とし、３３０〜２０００の範囲の分子量を有するものとする請求項 １記載の方法。2. The ozonolyzed polyolefin is a C2-C4 olefin polymer or A claim that the copolymer thereof has a molecular weight in the range of 330 to 2,000. The method described in 1. ３．前記工程（ａ）におけるポリオレフィンのオゾン分解を、溶剤中のポリオレ フィンの溶液を介して、付加的な希釈の有無によらず、気相中でのオゾンのバブ リングによって行う請求項１または２記載の方法。3. The ozonolysis of the polyolefin in step (a) is carried out using Bubbling of ozone in the gas phase, with or without additional dilution, through the solution of fins 3. The method according to claim 1, wherein the method is carried out by means of a ring. ４．オゾン分解温度を−７０〜＋５０℃とする請求項１乃至３いずれかに記載の 方法。4. According to any one of claims 1 to 3, the ozone decomposition temperature is -70 to +50°C. Method. ５．オゾン分解生成物と反応させるのに使用する第１ヒドロカルビルアミンを、 脂肪族、脂環式または芳香族の性状とし得る１以上のモノ、ジ並びにポリアミン から選択する請求項１乃至４いずれかに記載の方法。5. the primary hydrocarbylamine used to react with the ozonolysis products; one or more mono-, di-, and polyamines which may be aliphatic, cycloaliphatic or aromatic in character; 5. The method according to claim 1, wherein the method is selected from: ６．工程（ａ）に由来するオゾン分解生成物の反応を、５０〜２００℃の温度で 行う請求項１乃至５いずれかに記載の方法。6. The reaction of the ozonolysis products derived from step (a) is carried out at a temperature of 50 to 200 °C. The method according to any one of claims 1 to 5, wherein the method is carried out. ７．オゾン分解生成物と第１アミンとの反応において、２つのそれぞれのモル比 を１：１〜１０００：１とする請求項１乃至６いずれかに記載の方法。7. In the reaction of ozonolysis products with primary amines, the respective molar ratios of the two The method according to any one of claims 1 to 6, wherein the ratio is 1:1 to 1000:1. ８．工程（ｃ）に由来するイミンの水素添加を、ラネイニッケル、カーボン上の パラジウムまたはシリカ上のパラジウムのような触媒を使用して行う請求項１乃 至７いずれかに記載の方法。8. Hydrogenation of the imine derived from step (c) on Raney nickel, carbon Claim 1 carried out using a catalyst such as palladium or palladium on silica. The method described in any one of (7) to (7) above. ９．水素添加反応を２０ＭＰａまでの圧力で行う請求項１乃至８いずれかに記載 の方法。9. Claims 1 to 8, wherein the hydrogenation reaction is carried out at a pressure of up to 20 MPa. the method of. １０．水素添加反応を０〜２００℃の温度で行う請求項１乃至９いずれかに記載 の方法。10. Any one of claims 1 to 9, wherein the hydrogenation reaction is carried out at a temperature of 0 to 200°C. the method of.
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DE69003897T2 (en) 1994-02-10
EP0411084B1 (en) 1993-10-13
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NO904210D0 (en) 1990-09-27
WO1990009371A1 (en) 1990-08-23
ZA90872B (en) 1991-10-30
NO171058B (en) 1992-10-12
CA2009557A1 (en) 1990-08-10
DK0411084T3 (en) 1994-02-14
HUT57702A (en) 1991-12-30
HU901718D0 (en) 1991-11-28
EP0384086A1 (en) 1990-08-29
HU208666B (en) 1993-12-28
AU5028690A (en) 1990-09-05
SG123693G (en) 1994-02-25
DE69003897D1 (en) 1993-11-18
EP0411084A1 (en) 1991-02-06
AU622286B2 (en) 1992-04-02
AR245927A1 (en) 1994-03-30
US5103061A (en) 1992-04-07
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ATE95809T1 (en) 1993-10-15
NO171058C (en) 1993-01-20

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